Safe-handling perchlorate explosives

ABSTRACT

An explosive composition comprising a perchlorate and a solvent therefor, preferably a high boiling solvent in which the perchlorate is highly soluble.

tlnited States Patent 91 Klunsch et al.

SAFE-HANDLING PERCHLORATE EXPLOSIVES Inventors: Maximilian Klunsch, Opladen; Paul Lingens, Leverkusen; Heinz Ratz, Bonn-Ippendorf, all of Germany Assignee: Dynamit Nobel Aktiengellschaft, Troisdorf, Germany Filed: May 26, 1972 Appl. No.: 258,850

Foreign Application Priority Data 1 1 Feb. 4, 1975 [56] References Cited UNITED STATES PATENTS 2,899,468 8/1959 Cadle et al 149/36 X 2,951,335 9/1960 Stengel 149/36 3,431,155 3/1969 Dunglenson et a] 149/36 X 3,523,840 8/1970 Bedell 149/36 X 3,537,924 ll/l970 Byrne 149/36 3,586,553 6/1971 Fearnow 3,662,802 5/1972 Bedell 149/36 Primary Examiner-Leland A. Sebastian Assistant Examiner-13. A. Miller Attorney, Agent, or FirmRalph D. Dinklage; Burgess, Dinklage & Sprung [57] ABSTRACT An explosive composition comprising a perchlorate and a solvent therefor, preferably a high boiling solvent in which the perchlorate is highly soluble.

23 Claims, N0 Drawings SAFE-HANDLING PERCI-ILORATE EXPLOSIVES BACKGROUND OF THE INVENTION I. Field of the Invention This invention relates to safe-handling explosive mixtures. More particularly, this invention is directed to means for rendering perchloric acid containing explosive compositions less sensitive to friction and shock so that they can be used without danger. This invention is further directed to compositions containing perchlorate explosives in a mixture of solvents therefor.

2. Discussion of the Prior Art The present invention relates to safehandling explosive mixtures containing salts of perchloric acid which are explosive and sensitive to impact and shock.

It is known that the explosive, impact-and shocksensitive salts of perchloric acid, such as hydrazine perchlorate, methyl and dimethyl hydrazine perchlorate, mono-, diand trimethylamine perchlorate, ethanolamine perchlorate, ethylene diamine diperchlorate, onitroaniline perchlorate and pyridine perchlorate, for example, are high-energy explosives usually having an excellent detonatability. In practice, however, they are not used, on account of their great sensitivity to friction and shock. Even in explosives containing water, such as slurry explosives, they cannot be used without danger, although in this case they may be present in the dissolved state and hence in phlegmatized form. During storage, however, a portion of the water may evaporate from these explosives and the above-mentioned salts or perchloric acid might crystallize, resulting in an undersirable loss of safety against impact and shock.

If the hazardous salts of perchloric acid are in high concentration in the aqueous solution of the explosive, they might even crystallize upon the lowering of the temperature of the explosive.

SUMMARY OF THE INVENTION Broadly, this invention contemplates an explosive composition containing a perchlorate explosive and a solvent therefor.

More particularly, this invention contemplates an explosive composition containing a salt of perchloric acid and a high-boiling solvent therefor.

In accordance with this invention, it has been discovered that salts of perchloric acid useful as explosives can be rendered safe and useful as explosives by dissolving the perchlorate containing explosive compositions in a solvent therefor, preferably a high-boiling solvent for the explosive composition. Desirably the solvent is one in which the perchlorate explosive is highly soluble. Preferably the solvent is a high boiling point boiling at a temperature of at least I50C, preferably 190C determined at 1 atmospheric. It is desirable that the solvent have a high boiling point to maintain the solubility product constant, a measure of the solubility of the explosive composition in the solvent, at desirable levels. If the solubility product constant is exceeded due to evaporation of the solvent, the perchlorate explosive composition will crystallize out. When the same is in a crystal form as a precipitate it is highly dangerous as set forth below and accident due to impact or shock can occur. Since the solvent is desirably a high boiling or non-volatile solvent, the danger of the evaporation of the solvent is diminished. Hence crystallization of the salt of perchloric acid does not occur even after the explosive composition in the solvent is stored for extensive periods oftime at elevated temperatures, for example, 20 50C.

DESCRIPTION OF PREFERRED EMBODIMENTS The concentration of the salts of perchloric acid in the high boiling or non-volatile solvent is preferably selected in such a manner that no crystallization can occur in the climatic zone in which the explosive is to be used,.even at the lowest temperature which occurs in that zone. If other soluble salts, such as ammonium nitrate, are present in the explosive mixture, it is advantageous to determine whether the increase of the salt concentration in the solvent will result in the crystallization of the hazardous salts of perchloric acid or in the crystallization of salts of perchloric acid which are insensitive to impact and shock. such as ammonium perchlorate. A test for this can be performed by determining the impact sensitivity after subjecting the explosive mixture to varying temperatures. In this case, too, the concentration of the perchloric acid salts in the high boiling or non-volatile solvent is chosen such that no crystallization is obtained at the lowest temperature.

In principle, however, it is also possible to choose a lower concentration of the perchlorates in the solvent, although in that case a loss of energy must be reckoned with. Preferably the salt of perchloric acid is dissolved in the solvent in an amount between 1 and 50wt. percent, based on the weight of the solvent but preferably between 10 and 20 percent of the solubility product constant for the solute in the solvent under the applicable conditions of temperature and pressure.

High boiling solvents which can dissolve the explosive perchlorates and which can be used in accordance with the invention are polyvalent alcohols, amines and amides whose boiling point is above 150C. but preferably about lC, and which are able to dissolve the perchlorates, examples being l,2-ethanediol, 1,2- propanedrol, 1,2,3-propanetriol, the butanediols, or liquid aliphatically derived glycols of molecular weight between 76 and 2000. An example of a polyvalent ,amine is pentamethylenediamine. Formamide can also be used as a solvent according to the invention.

In these eutectic mixtures, ammonium nitrate is preferably used as the inorganic, orygen-yielding salt, and it can be replaced partially or even entirely by other alkali or alkaline earth nitrates or perchlorates. Additional inorganic, oxygen-yielding salts can be used in the non-volatile solvents employed pursuant to the invention.

The combustible compounds which lower the solidification point of these salts include the nitrates and perchlorates of amines and derivatives of ammonia. Primary, secondary and tertiary alkyl especially C,C alkyl groups and aryl amines e.g., single nucleus aryl amines, fused ring aryl amines and aryl amines containing two aryl groups joined at single carbon atoms e.g., a biphenyl amine. Examples of such amines include in particular ethylamine, aniline, phenylenediamine. Also contemplated are cyclic amines, e.g., hexamethylenetetramine, alkanolamines especially C -C alcohol amines or polyvalent amines e.g., ethylenediamine, hexamethylenediamine or tetraethylenepentamine, can be used as amines. The derivatives of ammonia include hydrazine, urea and its substitution products, urethanes, guanidines, and quaternary ammonium compounds, such as tetramethylammonium chloride,

tetramethylammonium sulfate,

tetramethylammonium nitrate,

tetraethylammonium chloride,

tetraethylammonium sulfate,

trimethylphenylammonium sulfate,

trimethylphenylammonium chloride, tetrapropylammonium sulfate, diphenyldimethylammonium chloride and the like, especially the quaternary ammonium compounds containing C -C alkyl groups pendant therefrom and aryl groups containing a single benzene nucleus.

Other combustible compounds which are suitable for lowering the freezing point are the ammonium salts of aliphatic carboxylic and sulfonic acids, especially those of aliphatic acids having between I and 8 carbon atoms, such as ammonium formate, ammonium acetate, ammonium sulfamate and the amides of these acids, such as formamide, and acetamide, urea and its derivatives such as urethanes and ureides, and carbamic acid.

Ammonium thiocyanate, ammonium hypophosphite, ammonium thiosulfate, anhydrous sodium acetate and monoand oligosaccharides are also suitable as combustible compounds which lower the freezing point.

To control consistency, swelling agents in quantities of0.l to 10 wt. percent, preferably l to 5 wt. percent, can be added to the eutectic mixtures serving as solvents. The swelling agents protect the perchlorate explosives made therefrom both against separation and against the penetration of water. Oligo-or polysaccharides are examples of swelling agents. The following are named as examples: guar flour, carob bean flour, agaragar, starch, cellulose derivatives (e.g., cellulose esters, ethers and glycolates), albuminous substances and gelatins, gum arabic, tragacanth or gum and alginates.

Thickening agents, such as polyacrylamide, polyacrylic acids, polyvinyl alcohol and polyoxymethylene can also serve as swelling agents; inert, finely divided thickening agents can also be used, such as bentonitcs, silicic acid and silicates such crystalline aluminosilicates especially those having pores.

in some cases the swelling agents may also be crosslinked. The swelling agents may be preserved by the addition of antibacterial agents, such as salicylic acid.

To permit the easier dissolving of the swelling agent, as much as percent water, with reference to the finished perchlorate explosive, can be added to the eutectic mixture.

The perchlorate explosive compositions which can be used in accordance with this invention generally include all of the known perchloric acids or perchlorate containing explosive compositions. Generally these are salts of perchloric acid and include the following:

hydrazine perchlorate,

methyl and dimethyl hydrazine perchlorate,

mono-, di and tri-methylamine perchlorate,

ethanolamine perchlorate,

ethylene diamine di-perchlorate,

orthonitroaniline perchlorate, and

pyridine perchlorate to name a few.

In order to more fully illustrate the nature of the invention in the manner of practicing the same, the following Examples are presented. In the Examples, all percentages are percentages by weight unless the contrary is indicated EXAMPLE 1 Table l gives the solubility of two impact and shock sensitive salts of perchloric acid in a number of solvents at 20C.

17% urea 15% ammonium nitrate It is seen from Table i that very appreciable amounts of the two hazardous salts of perchloric acid are soluble in the solvents used, at -20C. The explosive mixtures prepared with these solutions can be used wherever temperatures as low at 20C must be expected. Even after long standing at 20C, the two perchlorates have not crystallized out of the solvents. If the lowest temperature in other climatic zones is -l0C, 0C, +l0C or +20C, then 26, 29.3, 32.8 or 36 percent of hydrazine perchlorate can be dissolved in glycerine, for example. The detonatability and the energy of the two salts of perchloric acid become readily apparent in the solution of the low-melting, eutectic mixture: while the eutectic mixture produces no distension of the Trauzl lead block, a distension of 250 cm' /l0 g is obtained with the solution containing methylamine perchlorate, and a distension of 290 cm/l0 g is obtained with the solution containing hydrazine perchlorate.

EXAMPLE 2 An explosive composed of:

30% liquid, eutectic mixture,

0.1% guar flour 25.0% aluminum 44.9% ammonium nitrate in which the eutectic mixture consists of:

51% ethanolamine nitrate 17% methylamine nitrate,

17% urea and l5% ammonium nitrate produces a Trauzl lead block distension of 425 cm /l0 g. lfmethylamine perchlorate is dissolved in the liquid, eutectic mixture, so that it has the composition:

15.0% methylamine perchlorate 43.4% ethanolamine nitrate 14.4% methylamine nitrate 14.4% urea, and

12.8% ammonium nitrate, one obtains with the same explosive a lead block distension of 525 cm /lO g. This shows that the use of methylamine perchlorate in this explosive in accordance with the invention results in an appreciable increase in its energy. Even after 4 weeks of storage under alternating temperatures (24 hr at 50C, 24 hr at 20C), the impact sensitivity of the explosive mixture did not increase.

The explosive mixtures were prepared in the followmg manner:

The aqueous solution of ethanolamine and methylamine was neturalized with the corresponding amount of nitric acid and perchloric acid, respectively. After the addition of the calculated amounts of urea and ammonium nitrate, the water was removed by distillation in vacuo. The guar flour was stirred into the liquid, eutectic mixture at 80C. After cooling, the gelatines were mixed in the usual manner with aluminum and ammonium nitrate.

EXAMPLE 3 In this example it is shown how the detonatability of slurry-like, safe-handling explosives is improved by the addition of small amounts of the hazardous salts of perchloric acid. Table 2 gives the compositions and Trauzl lead block distensions for three explosive mixtures:

It is seen fromTable 2 that the explosive A virtually fails to react under the experimental conditions of the Trauzl lead block test. The substitution of 2.5 parts of methylamine perchlorate in the one case and 2.3 parts of hydrazine perchlorate in the other for 2.5 and 2.3 parts of ammonium nitrate, respectively, improves the detonatability of the explosive A to such an extent that definite lead block distensions are produced. After 4 weeks of alternating temperature storage (24 hr at 50C, 24 hr at C), a portion of the water had evaporated and the explosive mixture was no longer sludgelike. The impact sensitivity of mixtures B and C increased to the same extent as that of mixture A, that is, the impact sensitivity of mixtures B and C was not increased by the use of the hazardous salts of perchloric acid.

The terms and expressions used herein have been used as terms of description and not of limitation, as there is no intention, in the use of such terms and expressions, of excluding any equivalents, or portions thereof, as many modifications and departures are contemplated within the scope of the invention claimed. For instance, it is apparent that the crux of the present invention involves dissolving the perchlorate explosive composition in a solvent and maintaining it in the solvent in such form. The use of the solvent provides an explosive composition which is not dangerous in normal handling and yet provides a high amount of energy as seen in Example 3 above. It is apparent that numerous solvent compositions can be employed and that non-volatile eutectic compositions other than those specifically set forth above are contemplated.

A particularly effective eutectic composition useful in the present invention is disclosed in Ser. No. 259,353 filed concurrently herewith and now abandoned in favor of Ser. No. 413,720, filed Nov. 7, 1973, the disclosure of which is hereby incorporated herein by reference.

What is claimed is:

1. An explosive composition containing an explosive salt of perchloric acid which is sensitive to impact and shock and a solvent therefor, which solvent has a boiling point above C, said explosive salt of perchloric acid being dissolved in said solvent, said composition being such that the ingredients are present in such amount so that the solvent at 20C contains said explosive salt in dissolved liquid form, said composition exploding when detonated.

2. A composition according to claim 1, wherein said solvent is an alcohol, an amine or an amide having a boiling point above 150C.

3. A composition according to claim 2, wherein said solvent has a boiling point above C.

4. A composition according to claim 3, wherein said solvent is selected from the group consisting of 1,2- ethanediol, 1,2,3-propanetriol, butanediols, polyglycols, pcntamethylenediamine, and formamide.

5. An explosive composition according to claim 1 wherein said explosive salt of perchloric acid is selected from the group consisting of hydrazine perchlorate, methyl hydrazine perchlorate, dimethyl hydrazine perchlorate, monomethylamine perchlorate, dimethylamine perchlorate, trimethylamine perchlorate, ethanolamine perchlorate, ethylene diamine diperchlorate, onitroanaline perchlorate and pyridine perchlorate.

6. An explosive composition according to claim 1 wherein said solvent is selected from the group consisting of polyvalent alcohols, amines and amides.

7. An explosive composition according to claim 6 wherein said solvent is selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,2,3- propanetriol, butanediol and a liquid aliphatically derived glycol of molecular weight between 76 and 2000.

8. An explosive composition consisting essentially of:

a. an explosive salt of perchloric acid which is sensitive to impact and shock;

b. a liquid solvent of said explosive salt which solvent has a boiling point above 150C;

c. said liquid solvent consisting essentially of:

1. an oxygen yielding salt selected from the group consisting of ammonium nitrate, alkali metal nitrates, and alkaline earth metal nitrates; and

2. a combustible compound selected from the group consisting of a primary C -C alkylamine, a secondary C,C,=, alkylamine, a C -C tertiary amine, a single nucleus arylamine, a fused ring arylamine, an arylamine containing two aryl groups joined at a single carbon atom, a cyclic amine, hydrazine, urea, amides of aliphatic carboxylic acids, derivatives of urea, carbamic acid, urethanes, ureides, an alkanolamine, a polyvalent amine, guanidines, a quaternary ammonium compound, an ammonium salt of an aliphatic, carboxylic or sulfonic acid, ammonium thiocyanate, ammonium hypophosphite, ammonium thiosulfate, anhydrous sodium acetate, a monosaccharide, an oligosaccharide, a nitrate of amine, a derivative of ammonia and a perchlorate of an amine;

d. said composition being such that the ingredients are present in such amount so that the solvent at 20C contains said explosive salt in dissolved liquid form,

e. said composition exploding when detonated.

9. An explosive composition according to claim 8 wherein said oxygen yielding salt is ammonium nitrate.

10. A composition according to claim 8 wherein said explosive salt of perchloric acid is selected from the group consisting of hydrazine perchlorate, methyl hydrazine perchlorate, dimethyl hydrazine perchlorate, monomethylamine perchlorate, dimethylamine perchlorate, trimethylamine perchlorate, ethanolamine perchlorate. ethylene diamine diperchlorate, onitroanaline perchlorate and pyridine perchlorate.

II. A composition according to claim 8, wherein the oxygen-yielding salt in said liquid solvent is present in the two component mixture in an amount between and 70 percent by weight.

12. A composition according to claim 8, wherein said combustible compounds are selected from the group consisting of nitrates of amines. perchlorates of amines and derivatives of ammonia.

13. A composition according to claim 8, wherein said combustible compounds are selected from the group consisting of primary, secondary and tertiary alkyl and aryl amines, cyclic amines, alkanolamines and polyvalent amines and derivatives of ammonia.

14. A composition according to claim 8, wherein the combustible compounds are selected from the group consisting of primary, secondary and tertiary alkyl amines having from C -C carbon atoms in the alkyl group, aryl amines of a single nucleus, fused ring aryl groups and aryl groups wherein two aryl radicals are joined at single carbon atoms, urethanes, guanidines, quaternary ammonium compounds, alkanolamines having between 2 and 9 carbon atoms in the alkanolamine.

IS. A composition according to claim 8, wherein the combustible compound is selected from the group consisting of methylamine, ethylamine, analine, phenylenediamine, hexamethylenetetramine, ethylenediamine, hexamethylenediamine. tetraethylenepentamine, hydrazine, urea, tetramethylammonium chloride,

tetramethylammonium sulfate, tetramethylammonium nitrate, tetraethylammonium chloride, tetraethylammonium sulfate, trimethylphenylammonium sulfate, trimethylphenylammonium chloride, tetrapropylammonium sulfate and diphenyldimethylammonium chloride.

16. A composition according to claim 8, wherein the combustible compound is selected from the group consisting of ammonium salts of aliphatic carboxylic acids and ammonium salts of sulfonic acids.

17. A composition according to claim 16, wherein the ammonium salt ofthe aliphatic carboxylic acid is an ammonium salt of a carboxylic acid of an aliphatic group having between I and 8 carbon atoms.

18. A composition according to claim 16, wherein said ammonium salt is selected from the group consisting of ammonium formate, ammonium acetate and ammonium sulfamate.

19. A composition according to claim 8, wherein the combustible compound is selected from the group consisting of amides of aliphatic carboxylic acids, urea, derivatives of urea and carbamic acid.

20. A composition according to claim 8, wherein the combustible compound is selected from the group consisting of urethanes and ureides.

21. A composition according to claim 8, wherein the combustible compound is selected from the group consisting of ammonium thiocyanate, ammonium hypophosphite, ammonium thiosulfate, anhydrous sodium acetate. monosaccharides and oligosaccharides.

22. A composition according to claim 8, wherein said composition contains a swelling agent present in amount between (H and 10 percent based on the weight of the liquid solvent.

23. A composition according to claim 8, wherein said composition contains a thickening agent.

g g5? Um'n-m 51.7mm mum 1 UIFHtll-l Cl5l 'i[1."lCA'lE OF CORRECTION Pa tent No. 3 H Dated February 1975 Inven fl MAXIMILIAN KLfiNsca PA'LEL LINGENS: HEmz RATZ It is certified that error appears" in the ohmic-identified patent and that said Letters Patent are hereby corrected as shown below:

r- [75] Correct the. name of the inventor Klunsch to read Kliinsch umn 2, after line 42 and preceding line 43, insert the following paragraph Examples of non-volatile solvents that can be used according to the invention are low-melting,. eutectic mixtures of oxygen-yielding, inorganic salts and combustible compounds, which lower the freezing point of these salts. Such eutectic mixtures have a solidification point which may be lower than -lOC; they are especially suitable as solvents which can be utilized in accordance with the invention. Generally theinorganic salt is present in such mixtures in an amount between 5 and 70% by wt. preferably between 10 and 307. by wt.

Signed and Scaled this nineteenth D f Augusr1975 [SEAL] Attesr:

RUTH C. MASON C. MARSHALL DANN Alresring Officer (mnmissirmer ufPalenls and Trademark-A g 35' n umnn mun-4s mum 1' Uifl'ltll'l CERTUPICA'LE OF CORRECTION Patent No. 3,864,177 Dated r ary 4, 1975 lnvcnt fl MAXIMILJLAN KLllNSCH PAUL LINGENS, HEINZ BATZ It is certified that error appears in the show-identified patent Q and that said Letters Patent are hereby corrected as shown below:

F [75] (lorrect the. name of 'the inventor Klunsch to read Klunsch umn 2, after line 42 and preceding line 43, insert the following paragraph Examples of non-volatile solvents that can be used according to the invention are low-melting, eutectic mixtures of oxygen-yielding, inorganic salts and combustible compounds which lower the freezing point of these salts 9 Such eutectic mixtures have a solidification i t h' h p0 n w 1c may be lower than -l0C; they are especially suitable as solvents which can be utilized in accordance with the invention. Generally theinorganic salt is present in such mixtures in an amount between 5 and 707. by wt. preferably between 10 and 30% by wt.

Signed and Sealed this nineteenth D y of Augusf 9 5v [SEAL] Arrest:

, RUTH C. MASON C. MARSHALL DANN .-1!! Sling Officer (mnmissiun-er ofiarenls and Trademarks 

2. A composition according to claim 1, wherein said solvent is an alcohol, an amine or an amide having a boiling point above 150*C.
 2. a combustible compound selected from the group consisting of a primary C1-C5 alkylamine, a secondary C1-C5 alkylamine, a C1-C5 tertiary amine, a single nucleus arylamine, a fused ring arylamine, an arylamine containing two aryl groups joined at a single carbon atom, a cyclic amine, hydrazine, urea, amides of aliphatic carboxylic acids, derivatives of urea, carbamic acid, urethanes, ureides, an alkanolamine, a polyvalent amine, guanidines, a quaternary ammonium compouNd, an ammonium salt of an aliphatic, carboxylic or sulfonic acid, ammonium thiocyanate, ammonium hypophosphite, ammonium thiosulfate, anhydrous sodium acetate, a monosaccharide, an oligosaccharide, a nitrate of amine, a derivative of ammonia and a perchlorate of an amine; d. said composition being such that the ingredients are present in such amount so that the solvent at -20*C contains said explosive salt in dissolved liquid form; e. said composition exploding when detonated.
 3. A composition according to claim 2, wherein said solvent has a boiling point above 190*C.
 4. A composition according to claim 3, wherein said solvent is selected from the group consisting of 1,2-ethanediol, 1,2,3-propanetriol, butanediols, polyglycols, pentamethylenediamine, and formamide.
 5. An explosive composition according to claim 1 wherein said explosive salt of perchloric acid is selected from the group consisting of hydrazine perchlorate, methyl hydrazine perchlorate, dimethyl hydrazine perchlorate, monomethylamine perchlorate, dimethylamine perchlorate, trimethylamine perchlorate, ethanolamine perchlorate, ethylene diamine diperchlorate, o-nitroanaline perchlorate and pyridine perchlorate.
 6. An explosive composition according to claim 1 wherein said solvent is selected from the group consisting of polyvalent alcohols, amines and amides.
 7. An explosive composition according to claim 6 wherein said solvent is selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,2,3-propanetriol, butanediol and a liquid aliphatically derived glycol of molecular weight between 76 and
 2000. 8. An explosive composition consisting essentially of: a. an explosive salt of perchloric acid which is sensitive to impact and shock; b. a liquid solvent of said explosive salt which solvent has a boiling point above 150*C; c. said liquid solvent consisting essentially of:
 9. An explosive composition according to claim 8 wherein said oxygen yielding salt is ammonium nitrate.
 10. A composition according to claim 8 wherein said explosive salt of perchloric acid is selected from the group consisting of hydrazine perchlorate, methyl hydrazine perchlorate, dimethyl hydrazine perchlorate, monomethylamine perchlorate, dimethylamine perchlorate, trimethylamine perchlorate, ethanolamine perchlorate, ethylene diamine diperchlorate, o-nitroanaline perchlorate and pyridine perchlorate.
 11. A composition according to claim 8, wherein the oxygen-yielding salt in said liquid solvent is present in the two component mixture in an amount between 5 and 70 percent by weight.
 12. A composition according to claim 8, wherein said combustible compounds are selected from the group consisting of nitrates of amines, perchlorates of amines and derivatives of ammonia.
 13. A composition according to claim 8, wherein said combustible compounds are selected from the group consisting of primary, secondary and tertiary alkyl and aryl amines, cyclic amines, alkanolamines and polyvalent amines and derivatives of ammonia.
 14. A composition according to claim 8, wherein the combustible compounds are selected from the group consisting of primary, secondary and tertiary alkyl amines having from C1-C5 carbon atoms in the alkyl group, aryl amines of a single nucleus, fused ring aryl groups and aryl groups wherein two aryl radicals are joined at single carbon atoms, urethanes, guanidines, quaternary ammonium compounds, alkanolamines having between 2 and 9 carbon atoms in the alkanolamine.
 15. A composition according to claim 8, wherein the combustible compound is selected from the group consisting of methylamine, ethylamine, analine, phenylenediamine, hexamethylenetetramine, ethylenediamine, hexamethylenediamine, tetraethylenepentamine, hydrazine, urea, tetramethylammonium chloride, tetramethylammonium sulfate, tetramethylammonium nitrate, tetraethylammonium chloride, tetraethylammonium sulfate, trimethylphenylammonium sulfate, trimethylphenylammonium chloride, tetrapropylammonium sulfate and diphenyldimethylammonium chloride.
 16. A composition according to claim 8, wherein the combustible compound is selected from the group consisting of ammonium salts of aliphatic carboxylic acids and ammonium salts of sulfonic acids.
 17. A composition according to claim 16, wherein the ammonium salt of the aliphatic carboxylic acid is an ammonium salt of a carboxylic acid of an aliphatic group having between 1 and 8 carbon atoms.
 18. A composition according to claim 16, wherein said ammonium salt is selected from the group consisting of ammonium formate, ammonium acetate and ammonium sulfamate.
 19. A composition according to claim 8, wherein the combustible compound is selected from the group consisting of amides of aliphatic carboxylic acids, urea, derivatives of urea and carbamic acid.
 20. A composition according to claim 8, wherein the combustible compound is selected from the group consisting of urethanes and ureides.
 21. A composition according to claim 8, wherein the combustible compound is selected from the group consisting of ammonium thiocyanate, ammonium hypophosphite, ammonium thiosulfate, anhydrous sodium acetate, monosaccharides and oligosaccharides.
 22. A composition according to claim 8, wherein said composition contains a swelling agent present in amount between 0.1 and 10 PERCENT based on the weight of the liquid solvent.
 23. A composition according to claim 8, wherein said composition contains a thickening agent. 